CN114182094A - Comprehensive recycling method for valuable metals in hard alloy grinding material - Google Patents
Comprehensive recycling method for valuable metals in hard alloy grinding material Download PDFInfo
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- CN114182094A CN114182094A CN202111085991.4A CN202111085991A CN114182094A CN 114182094 A CN114182094 A CN 114182094A CN 202111085991 A CN202111085991 A CN 202111085991A CN 114182094 A CN114182094 A CN 114182094A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a comprehensive recycling method of valuable metals in a hard alloy grinding material, which comprises the following steps: preparing dilute sulfuric acid in a reaction tank, adding a hard alloy grinding material, adding a small amount of sodium chlorate solution under the stirring state until the temperature of the material liquid rises to be above 80 ℃, dispersing and introducing air into the material liquid for oxidation reaction until metals except tungsten carbide in the grinding material are completely dissolved, stopping the reaction when the pH reaches 0.5-1, filtering and washing to obtain filtrate A and filter residue A, wherein the filter residue A is tungsten carbide and can be directly sold after being dried, adding water into the filtrate A to adjust the baume degree of the filtrate to 10-12 degrees B and precipitating for 8-10 hours, so that tungstic acid precipitate is separated from tungsten sol in the solution; recovering copper, iron, cobalt and nickel from the filtrate after recovering the tungstic acid; after the method is adopted to recover valuable elements, the recovery rates of tungsten, copper, cobalt and nickel in the hard alloy grinding material reach more than 99 percent, which is higher than the common level in the same industry, and the method has the advantages of simple process and low treatment cost.
Description
Technical Field
The invention relates to the technical field of environment-friendly recovery of hard alloy grinding materials, in particular to a comprehensive recycling method of valuable metals in a hard alloy grinding material.
Background
Cemented carbide tool materials are an alloy material made from a high hardness, refractory metal compound tungsten carbide powder and a metal binder (e.g., Co, Ni, Cu, etc.) by a powder metallurgy process. The hard alloy has a series of excellent performances of high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, particularly high hardness and wear resistance, basically keeps unchanged even at the temperature of 500 ℃, and still has high hardness at the temperature of 1000 ℃. Cemented carbide is widely used as a tool material, such as turning tools, milling cutters, planing tools, drill bits, boring tools and the like, for cutting cast iron, nonferrous metals, plastics, chemical fibers, graphite, glass, stone and common steel, and also for cutting refractory steel, stainless steel, high manganese steel, tool steel and other materials which are difficult to process.
The hard alloy grinding material is a waste material generated in the process of machining a cutter, and mainly contains valuable metal elements as follows: tungsten (in the form of tungsten carbide), cobalt, and small amounts of nickel and copper.
Conventionally, when a cemented carbide abrasive is recovered, the abrasive is added to a sulfuric acid solution, and an oxidizing agent such as sodium chlorate is added to perform oxidation and acid leaching, whereby metals other than tungsten carbide are dissolved to produce sulfate, thereby separating tungsten from other metals and further recovering various valuable metal elements. However, actual production finds that when the method is used for recovery, a small amount of tungsten carbide is oxidized to form tungsten sol under the action of a strong oxidant and the tungsten sol exists in a solution and is difficult to recover, so that the recovery rate of tungsten can only reach 95%, and the reason why the recovery rate of tungsten can only reach 95% is not clear to professionals in the industry. And because of the existence of the tungsten sol, the recovery rate is not high when copper, cobalt and nickel elements are recovered subsequently.
Disclosure of Invention
The method of the invention is to solve the problems that the recovery rate of tungsten element is not high and the recovery rate of other metals is not high when sulfuric acid and sodium chlorate oxidation acid leaching are adopted to recover valuable elements in the hard alloy grinding material at present, and provides a comprehensive recovery and utilization method of valuable metals in the hard alloy grinding material, the method of the invention adopts a method of diluting and adjusting the proportion of solution, so that tungsten sol in feed liquid is hydrolyzed, tungstic acid precipitate is separated out and is easy to filter, and the high recovery rate (more than 99%) of tungsten is effectively ensured; by adopting the method, the valuable metals in the hard alloy grinding material can be recovered with the maximum efficiency, and the recovery process is simple and efficient and has high economic benefit.
The invention relates to a comprehensive recycling method of valuable metals in a hard alloy grinding material, which comprises the following steps:
(1) adding water into a reaction tank, adding 98% concentrated sulfuric acid by mass to prepare 15-25% dilute sulfuric acid by mass, adding a hard alloy grinding material into the reaction tank, wherein the mass ratio of the concentrated sulfuric acid to the hard alloy grinding material is 0.9-1.0:1, adding a small amount of sodium chlorate solution under a stirring state, quickly raising the temperature of the material liquid to over 80 ℃ under the action of an exothermic reaction, dispersing and introducing air into the material liquid for an oxidation reaction, stopping the reaction when all metals except tungsten carbide in the grinding material are dissolved and the pH value reaches 0.5-1, filtering and washing to obtain a filtrate A and a filter residue A, wherein the filter residue A is tungsten carbide, and can be directly sold after being dried, and the filtrate A continues to perform the next reaction;
(2) adding water into the filtrate A to adjust the baume degree of the filtrate to 10-12 Be and precipitating for 8-10 hours, separating out tungstic acid precipitate from the solution, and filtering after the solution is clear and transparent to obtain filtrate B and filter residue B, wherein the filter residue is tungstic acid which can be sold directly; continuing the next step of treatment on the filtrate B;
(3) detecting the copper content in the filtrate B, adding equivalent sodium sulfide according to the copper content, stirring for reaction for 15-30 minutes, converting copper into dilute acid-insoluble copper sulfide precipitate under an acidic condition, and filtering to obtain filtrate C and filter residue C, wherein the filter residue C is the copper sulfide exterior sales treatment; continuing the next step of treatment on the filtrate C;
(4) adding alkali into the filtrate C to adjust the pH value to 4-5, converting iron into ferric hydroxide precipitate, and filtering to obtain filtrate D and filter residue D, wherein the filter residue D is treated as solid waste; continuing the next step of treatment on the filtrate D;
(5) adding sodium carbonate into the filtrate D to neutralize until the pH value is 7.5-8, precipitating cobalt and nickel in the form of cobalt carbonate and nickel carbonate, filtering and washing to obtain a mixture of cobalt carbonate and nickel carbonate, and selling the mixture to cobalt and nickel product manufacturers for extraction and separation to produce cobalt and nickel products; the filtrate is wastewater containing a small amount of sodium chloride and sodium sulfate and is sent to sewage treatment.
The hard alloy grinding material is nitric acid soluble powder with the mass fraction of 38.6 percent, wherein the nitric acid soluble powder contains 58-62 percent (wt) of tungsten carbide, 0.5-0.7 percent (wt) of copper, 8-12 percent (wt) of cobalt and 0.5-0.7 percent (wt) of nickel.
The method of the invention is to add sulfuric acid into the hard alloy grinding material, add sodium chlorate, inject air and other oxidation conditions to oxidize and acid-leach, dissolve metals except tungsten carbide, produce sulfate which is easy to dissolve in water, filter and reclaim tungsten carbide, and in the above-mentioned oxidizing and acid-leaching process, there is a small amount of tungstic acid produced in the solution (because a small amount of tungsten carbide is oxidized and produced), the tungstic acid produced enters the solution in the form of colloid, it is difficult to reclaim through the method of filtering, and this problem, have not found in the recovery technology in the past, cause the tungsten recovery rate to be low in the industry for a long time. The inventor of the invention finds the key problem just after repeatedly researching the recovery process of the hard alloy grinding material, so the invention also designs the recovery step of the tungstic acid colloid after filtering and recovering the tungsten carbide, and solves the problem. And removing tungstic acid from the filtrate, and then sequentially recovering copper, iron, cobalt and nickel, thereby perfectly completing the recovery of valuable metals in the hard alloy grinding material. The invention also aims to solve the problem that the colloid tungstic acid must be recovered before the cobalt, nickel and copper are recovered.
The main chemical reaction involved in the above process is as follows:
the grinding material is dissolved in a sulfuric acid medium by oxidation to generate sulfate, and the main chemical reaction formula is as follows:
2Co+2H2SO4+O2=2CoSO4+2H2O；
2Ni+2H2SO4+O2=2NiSO4+2H2O；
2Cu+2H2SO4+O2=2CuSO4+2H2O；
2Co+2H2SO4+O2=2CoSO4+2H2O；
3Co+3H2SO4+NaClO3=3CoSO4+NaCl+3H2O；
3Ni+3H2SO4+NaClO3=3NiSO4+NaCl+3H2O；
3Cu+3H2SO4+NaClO3=3CuSO4+NaCl+3H2O；
Fe+H++O2→2Fe3+；
Fe3++Co+H+→Co2++Fe2+；
Fe2++H++O2→Fe3+；
Fe3++Ni+H+→Ni2++Fe2+；
Cu2++S2-→CuS↓；
Fe3++OH- =Fe（OH）3↓；
CoSO4+Na2CO3=CoCO3↓+Na2SO4；
NiSO4+Na2CO3=NiCO3↓+Na2SO4。
in the invention, oxygen is not introduced during the oxidation acid leaching, and only a sodium chlorate adding mode is adopted for the oxidation acid leaching; separating tungstic acid colloid together with tungsten carbide precipitate, during the specific operation, directly adding water to adjust the baume degree of the solution to 10-12 DEG Be after the oxidation and acid leaching of the rest metal powder in the hard alloy, standing for 8-10 hours, filtering again, namely separating tungstic acid and tungsten carbide at one time, and then extracting copper, iron, cobalt and nickel subsequently.
The invention points of the method mainly comprise the following two points: 1. the method solves the problems that a small amount of tungstic acid colloid generated in the oxidation and acid leaching processes of the hard alloy grinding material is difficult to recover, and the recovery rate of tungsten and the recovery rate of other valuable metal elements are influenced; 2. air is introduced during acid leaching, so that the use amount of sodium chlorate is saved, and the production cost is reduced.
The method is scientific and environment-friendly, has simple production process and low production cost, solves the problem of low tungsten recovery rate which is perplexed in the industry for a long time, breaks a new technical barrier for the recovery and utilization of valuable metal elements in the hard alloy grinding material, improves the economic benefit of enterprises, and is suitable for wide popularization and use. After the valuable elements are extracted and recovered by the method, the recovery rate of tungsten, copper, cobalt and nickel in the hard alloy grinding material can reach more than 99 percent, which shows that the recovery rate of the valuable elements is improved compared with the traditional method.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The process of the present invention is further illustrated by the following specific examples, which are intended to be purely exemplary and are not intended to limit the invention in any way.
Example 1
A comprehensive recycling method of valuable metals in hard alloy grinding materials comprises the following steps:
(1) adding 1000ml of water into a 2000ml three-necked bottle, adding 125g of concentrated sulfuric acid with the mass fraction of 98%, adding 132g of hard alloy grinding material (38.6% nitric acid dissolved matter with the tungsten carbide content of 61%, the copper content of 0.61%, the cobalt content of 10.01% and the nickel content of 0.59%) under stirring, slowly adding 63ml of sodium chlorate with the mass fraction of 50%, stirring and reacting for 1h, adding water to dilute the solution until the baume degree of the solution is 11 ° Be when the pH value reaches 0.5, standing for 8 h, filtering and washing to obtain filter residue A and filtrate A, and drying the filter residue to obtain 79.86g of tungsten carbide powder (containing a small amount of tungstic acid);
(2) detecting the copper content in the filtrate A to be 0.78g, adding 1.6g of sodium sulfide with the mass fraction of 60%, stirring and reacting for 15 minutes, filtering and washing to obtain filter residue B and filtrate B, drying the filter residue B at 60 ℃ to obtain 1.21g of copper sulfide with the copper content of 65.87%, and carrying out the next operation on the filtrate B;
(3) adding sodium carbonate into the filtrate B to adjust the pH of the solution to 4.0, filtering and washing to obtain filter residue C which is ferric hydroxide, and discarding; continuing to perform the next operation on the filtrate C;
(4) and continuously adding sodium carbonate into the filtrate C to adjust the pH value of the solution to 7.5, continuously stirring for 30min, filtering, washing and drying to obtain 34.23g of a cobalt carbonate and nickel carbonate mixture, wherein the cobalt content is 38.26g, the nickel content is 2.25%, and discarding the filtrate.
After the valuable elements are extracted and recovered by the method of the embodiment, in the embodiment, the recovery rate of W is 99.2%, the recovery rate of copper is 99%, the recovery rate of cobalt is 99.15%, and the recovery rate of nickel is 98.8%, which shows that the recovery rate of the valuable elements is improved compared with the conventional method.
Example 2
Referring to fig. 1, a comprehensive recycling method of valuable metals in a hard alloy grinding material comprises the following steps:
(1) adding 1500kg of water into a 3000L reaction tank, adding 520kg of concentrated sulfuric acid with the mass fraction of 98%, adding 550kg of hard alloy grinding material (38.6% nitric acid dissolved matter, wherein the content of WC is 61%, the content of copper is 0.61%, the content of cobalt is 10.01%, and the content of nickel is 0.59%), adding 50% of sodium chlorate solution with the mass fraction under the stirring state until the temperature of the reaction solution reaches more than 80 ℃, stopping adding sodium chlorate at the moment, dispersedly introducing compressed air to oxidize and pickle until the tungsten carbide powder precipitation meets the requirements (adding a small amount of tungsten carbide powder precipitation into dilute sulfuric acid, adding hydrogen peroxide into the solution, and filtering to obtain filtrate A and filter residue A, drying the filter residue A to obtain 322.2kg of tungsten carbide, and directly selling the tungsten carbide; continuing to perform next treatment on the filtrate A;
(2) adding water into the filtrate A to adjust the baume degree of the filtrate to 10 Bee, precipitating for 10 hours, separating out tungstic acid precipitate from the solution, filtering after the solution is clear and transparent to obtain filtrate B and filter residue B, drying the filter residue to obtain 20.4kg of tungstic acid, wherein the W content is 65.1 percent, and the tungstic acid can be directly sold; continuing the next step of treatment on the filtrate B;
(3) detecting and calculating the copper content in the filtrate B to be 3.34Kg, adding 6.9Kg of sodium sulfide with the mass fraction of 60%, stirring and reacting for 30 minutes, converting copper into copper sulfide precipitate under an acidic condition, filtering to obtain filtrate C and filter residue C, drying the filter residue C to obtain 5.1Kg of copper sulfide, wherein the copper content is 65.47%, and directly selling the copper sulfide; continuing the next step of treatment on the filtrate C;
(4) adding sodium carbonate into the filtrate C to adjust the pH value to 4.5, converting iron into ferric hydroxide precipitate, and filtering to obtain filtrate D and filter residue D, wherein the filter residue D is ferric hydroxide and is directly treated as solid waste; continuing the next step of treatment on the filtrate D;
(5) adding sodium carbonate into the filtrate D to neutralize the pH value of the filtrate to 8, continuously stirring for 30 minutes, precipitating cobalt and nickel in the form of cobalt carbonate and nickel carbonate, filtering and washing, drying filter residues to obtain 139.8kg of a mixture of cobalt carbonate and nickel carbonate, wherein the cobalt content is 39.1 percent, the nickel content is 2.3 percent, and the cobalt carbonate and nickel carbonate is sold to cobalt and nickel product manufacturers for extraction and separation to produce cobalt and nickel products; the filtrate is wastewater containing a small amount of sodium chloride and sodium sulfate and is sent to sewage treatment.
After the valuable elements are extracted and recovered by the method of the embodiment, in the embodiment, the recovery rate of W is 99.9%, the recovery rate of copper is 99.5%, the recovery rate of cobalt is 99.3%, and the recovery rate of nickel is 99.5%, which shows that the recovery rate of the valuable elements is improved by the method of the invention compared with the traditional method.
Example 3
A comprehensive recycling method of valuable metals in hard alloy grinding materials comprises the following steps:
(1) adding 1500kg of water into a 3000L reaction tank, adding 650kg of 98% concentrated sulfuric acid, adding 688kg of hard alloy grinding material (38.6% nitric acid dissolved matter, wherein the WC content is 61%, the copper content is 0.61%, the cobalt content is 10.01%, and the nickel content is 0.59%), adding 50% sodium chlorate solution in a stirring state until the temperature of the reaction solution reaches above 80 ℃, stopping adding sodium chlorate at the moment, dispersedly introducing compressed air to oxidize and pickle until tungsten carbide powder precipitates meet the requirements, filtering to obtain filtrate A and filter residue A, drying the filter residue A to obtain 402.5kg of tungsten carbide, and directly selling the tungsten carbide powder; continuing to perform next treatment on the filtrate A;
(2) adding water into the filtrate A to adjust the baume degree of the filtrate to 12 Be and precipitating for 9 hours, separating out tungstic acid precipitate from the solution, filtering after the solution is clear and transparent to obtain filtrate B and filter residue B, drying the filter residue to obtain 26.3kg of tungstic acid, wherein the content of W is 64.8 percent, and the tungstic acid can be directly sold; continuing the next step of treatment on the filtrate B;
(3) detecting and calculating the copper content in the filtrate B to be 4.2Kg, adding 8.6Kg of sodium sulfide with the mass fraction of 60 percent into the filtrate B, stirring the mixture to react for 20 minutes, converting the copper into copper sulfide precipitate under an acidic condition, filtering the copper sulfide precipitate to obtain filtrate C and filter residue C, drying the filter residue C to obtain 6.36Kg of copper sulfide, wherein the copper content is 65.68 percent, and directly selling the copper sulfide and the filter residue C; continuing the next step of treatment on the filtrate C;
(4) adding sodium carbonate into the filtrate C to adjust the pH value to 5.0, converting iron into ferric hydroxide precipitate, and filtering to obtain filtrate D and filter residue D, wherein the filter residue D is ferric hydroxide and is directly treated as solid waste; continuing the next step of treatment on the filtrate D;
(5) adding sodium carbonate into the filtrate D to neutralize the pH value of the filtrate to 7.8, continuously stirring for 30 minutes, precipitating cobalt and nickel in the form of cobalt carbonate and nickel carbonate, filtering and washing, drying filter residues to obtain 175.2kg of a mixture of cobalt carbonate and nickel carbonate, wherein the cobalt content is 38.95 percent, the nickel content is 2.29 percent, and selling the mixture to cobalt and nickel product production enterprises for extraction and separation to produce cobalt and nickel products; the filtrate is wastewater containing a small amount of sodium chloride and sodium sulfate and is sent to sewage treatment.
After the valuable element extraction and recovery are carried out by the method of the embodiment, in the embodiment, the recovery rate of W is 99.8%, the recovery rate of copper is 99.6%, the recovery rate of cobalt is 99.1%, and the recovery rate of nickel is 98.82%, which shows that the recovery rate of the valuable element is improved by the method of the invention compared with the traditional method.
The above-described embodiments are not intended to limit the present invention in any way, and any process scheme which is the same as or similar to the process scheme of the present invention and is carried out under the principle of the claims of the present invention is considered to fall within the protection scope of the claims of the present invention.
Claims (2)
1. A comprehensive recycling method of valuable metals in hard alloy grinding materials is characterized by comprising the following steps:
(1) adding water into a reaction tank, adding 98% concentrated sulfuric acid by mass to prepare 15-25% dilute sulfuric acid by mass, adding a hard alloy grinding material into the reaction tank, wherein the mass ratio of the concentrated sulfuric acid to the hard alloy grinding material is 0.9-1.0:1, adding a small amount of sodium chlorate solution under a stirring state, quickly raising the temperature of the material liquid to over 80 ℃ under the action of an exothermic reaction, dispersing and introducing air into the material liquid for an oxidation reaction, stopping the reaction when all metals except tungsten carbide in the grinding material are dissolved and the pH value reaches 0.5-1, filtering and washing to obtain a filtrate A and a filter residue A, wherein the filter residue A is tungsten carbide, and can be directly sold after being dried, and the filtrate A continues to perform the next reaction;
(2) adding water into the filtrate A to adjust the baume degree of the filtrate to 10-12 Be and precipitating for 8-10 hours, separating out tungstic acid precipitate from the solution, and filtering after the solution is clear and transparent to obtain filtrate B and filter residue B, wherein the filter residue is tungstic acid which can be sold directly; continuing the next step of treatment on the filtrate B;
(3) detecting the copper content in the filtrate B, adding equivalent sodium sulfide according to the copper content, stirring for reaction for 15-30 minutes, converting copper into dilute acid-insoluble copper sulfide precipitate under an acidic condition, and filtering to obtain filtrate C and filter residue C, wherein the filter residue C is the copper sulfide exterior sales treatment; continuing the next step of treatment on the filtrate C;
(4) adding alkali into the filtrate C to adjust the pH value to 4-5, converting iron into ferric hydroxide precipitate, and filtering to obtain filtrate D and filter residue D, wherein the filter residue D is treated as solid waste; continuing the next step of treatment on the filtrate D;
(5) adding sodium carbonate into the filtrate D to neutralize until the pH value is 7.5-8, precipitating cobalt and nickel in the form of cobalt carbonate and nickel carbonate, filtering and washing to obtain a mixture of cobalt carbonate and nickel carbonate, and selling the mixture to cobalt and nickel product manufacturers for extraction and separation to produce cobalt and nickel products; the filtrate is wastewater containing a small amount of sodium chloride and sodium sulfate and is sent to sewage treatment.
2. The method for comprehensively recycling valuable metals in the hard alloy grinding material according to claim 1, characterized by comprising the following steps: the hard alloy grinding material is nitric acid soluble powder with the mass fraction of 38.6 percent, wherein the nitric acid soluble powder contains 58-62 percent (wt) of tungsten carbide, 0.5-0.7 percent (wt) of copper, 8-12 percent (wt) of cobalt and 0.5-0.7 percent (wt) of nickel.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186969A (en) * | 2007-12-25 | 2008-05-28 | 北大方正集团有限公司 | Method for separating rare earth, iron, copper, cobalt and tungsten from alloy |
| KR20110032033A (en) * | 2009-09-22 | 2011-03-30 | 리컴 주식회사 | Recovery of tungsten and cobalt from hardmetal alloy sludge by the hydrometallurgical process using aqua regia |
| CN103911514A (en) * | 2013-01-06 | 2014-07-09 | 中石化上海工程有限公司 | Waste hard alloy grinding material recovery treatment method |
| CN106498172A (en) * | 2016-12-14 | 2017-03-15 | 荆门市格林美新材料有限公司 | Hard-alloy grinding material tungsten-cobalt disperses the recovery method of tungsten in separating |
| KR20170032906A (en) * | 2015-08-26 | 2017-03-24 | 한국기계연구원 | Recovery method of tungsten compound from waste hard metal |
| CN110629052A (en) * | 2019-09-16 | 2019-12-31 | 厦门钨业股份有限公司 | Method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste |
-
2021
- 2021-09-16 CN CN202111085991.4A patent/CN114182094A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186969A (en) * | 2007-12-25 | 2008-05-28 | 北大方正集团有限公司 | Method for separating rare earth, iron, copper, cobalt and tungsten from alloy |
| KR20110032033A (en) * | 2009-09-22 | 2011-03-30 | 리컴 주식회사 | Recovery of tungsten and cobalt from hardmetal alloy sludge by the hydrometallurgical process using aqua regia |
| CN103911514A (en) * | 2013-01-06 | 2014-07-09 | 中石化上海工程有限公司 | Waste hard alloy grinding material recovery treatment method |
| KR20170032906A (en) * | 2015-08-26 | 2017-03-24 | 한국기계연구원 | Recovery method of tungsten compound from waste hard metal |
| CN106498172A (en) * | 2016-12-14 | 2017-03-15 | 荆门市格林美新材料有限公司 | Hard-alloy grinding material tungsten-cobalt disperses the recovery method of tungsten in separating |
| CN110629052A (en) * | 2019-09-16 | 2019-12-31 | 厦门钨业股份有限公司 | Method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste |
Non-Patent Citations (1)
| Title |
|---|
| 潘长华: "实用小化工生产大全", 化学工业出版社, pages: 207 * |
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